CN111463483A - Preparation method and formula of lithium borate-containing lithium ion battery electrolyte - Google Patents
Preparation method and formula of lithium borate-containing lithium ion battery electrolyte Download PDFInfo
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- CN111463483A CN111463483A CN202010355861.7A CN202010355861A CN111463483A CN 111463483 A CN111463483 A CN 111463483A CN 202010355861 A CN202010355861 A CN 202010355861A CN 111463483 A CN111463483 A CN 111463483A
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- ion battery
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- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 44
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 17
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 14
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000004364 calculation method Methods 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 7
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 23
- 238000009924 canning Methods 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 10
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 8
- 238000004904 shortening Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 4
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F21/00—Dissolving
- B01F21/02—Methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F21/00—Dissolving
- B01F21/10—Dissolving using driven stirrers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of lithium ion battery electrolyte containing lithium borate, which comprises the following steps: s1, selecting a first solvent to carry out heating mixing pretreatment on lithium borate to form a mixed solution containing lithium borate, wherein the first solvent is one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate or dimethyl carbonate; s2, preparing electrolyte: adding a second solvent, a mixed solution containing lithium borate and an additive into a stirring kettle by calculation, uniformly mixing, then adding lithium hexafluorophosphate, uniformly mixing, filling and warehousing; the invention also provides three formulas of lithium ion battery electrolytes containing lithium borate; the method for pretreating the lithium borate has the advantages of no occupation of stirring production time, shortened production process, no influence on canning duration and high production efficiency, and the mode of raising the temperature to dissolve the lithium borate in the pretreatment can improve the dissolution rate and the stability of the lithium borate in a solvent and ensure the excellent quality of the electrolyte.
Description
Technical Field
The invention relates to a preparation method and a formula of lithium ion battery electrolyte, in particular to a preparation method and a formula of lithium ion battery electrolyte containing lithium borate.
Background
In the traditional production method, all materials in the electrolyte formula are sequentially added into a reaction kettle for mixing and stirring, and the reaction kettle needs to be controlled at a low temperature of 5-15 ℃ to ensure the product quality because lithium hexafluorophosphate is unstable and can quickly release heat in the dissolving process. However, lithium borate is stable and low in solubility at normal temperature or low temperature, so that the lithium borate needs to be mixed and dissolved at high temperature, and if the lithium borate is produced by using the same reaction kettle, the process of repeatedly heating and cooling can be involved, so that the preparation method in the prior art has the technical problems of complex operation, long production process, low production efficiency, high energy consumption, easy precipitation of lithium borate, easy turbidity of electrolyte and incapability of ensuring the quality of electrolyte.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and a formula of lithium borate-containing lithium ion battery electrolyte, which are used for carrying out pretreatment on lithium borate in advance, improving the dissolution rate and the stability of the lithium borate in a solvent, preventing the lithium borate from being separated out in the placing process of the electrolyte, avoiding the turbidity of the electrolyte, ensuring the quality of the electrolyte, greatly shortening the preparation and production procedures and improving the production efficiency.
In order to achieve the aim, the invention provides a preparation method of lithium ion battery electrolyte containing lithium borate, which comprises the following steps:
s1, selecting a proper first solvent to carry out pretreatment on the lithium borate: heating and mixing a first solvent and lithium borate, wherein the temperature of a reaction kettle is 60-90 ℃ during mixing, the stirring time is 1-3 hours, and the first solvent can be one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, propyl propionate or dimethyl carbonate;
if ethylene carbonate is selected as a first solvent for lithium borate pretreatment, the stirring kettle needs to be kept in a heat preservation state all the time to form a mixed solution containing lithium borate;
if other substances are selected as the first solvent for lithium borate pretreatment, the mixed solution is stirred and mixed uniformly and then needs to be cooled naturally to form a mixed solution containing lithium borate;
s2, preparing lithium ion battery electrolyte containing lithium borate: and (4) sequentially adding the second solvent, the mixed solution containing the lithium borate and the additive in the step S1 into the stirring kettle by calculation, mixing and stirring for 30 minutes, adding lithium hexafluorophosphate after uniformly mixing, filling and warehousing after uniformly mixing.
Preferably, the lithium borate in step S1 is one or both of lithium bis (oxalato) borate and lithium difluoro (oxalato) borate.
Preferably, the additive in step S2 is a mixture of two or more of propylene sulfate, fluoroethylene carbonate, vinylene carbonate and lithium bis-fluorosulfonylimide.
Preferably, the second solvent in step S2 is a mixture of three or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, propyl propionate and carboxylic acid ester.
Preferably, the first solvent described in step S1 is ethylene carbonate.
Preferably, the second solvent described in step S2 is a mixture of ethylene carbonate, diethyl carbonate and propylene carbonate.
Preferably, the second solvent described in step S2 is ethylene carbonate, ethyl methyl carbonate, propyl propionate, or propylene carbonate.
Compared with the prior art, the preparation method of the lithium ion battery electrolyte containing the lithium borate has the beneficial effects that:
the lithium ion battery electrolyte is produced by adopting a lithium borate pretreatment method, so that the method has the advantages of not occupying the production time of mixing and stirring, greatly shortening the production process, not influencing the canning time and having high production efficiency, and the lithium borate dissolution rate and the stability in a solvent can be improved by increasing the temperature in the pretreatment, so that the excellent quality of the electrolyte is ensured.
The invention also provides a formula of the lithium ion battery electrolyte containing lithium borate, which is prepared by the preparation method of the lithium ion battery electrolyte containing lithium borate, wherein the lithium ion battery electrolyte is prepared by mixing lithium hexafluorophosphate, lithium difluorooxalate borate, ethylene carbonate, diethyl carbonate, propylene carbonate, ethylene sulfate and fluoroethylene carbonate in a ratio of 135: 8-12: 230-240: 465-475: 115-125: 5-50: 10 to 100 by mass ratio.
The invention also provides a formula of a second lithium-ion battery electrolyte containing lithium borate, which is prepared by the preparation method of the lithium-ion battery electrolyte containing lithium borate, and the lithium-ion battery electrolyte is prepared by mixing lithium hexafluorophosphate, lithium difluorooxalate borate, lithium difluorosulfonimide, ethylene carbonate, ethyl methyl carbonate, propyl propionate, propylene carbonate, ethylene sulfate and fluoroethylene carbonate in a proportion of 130: 8-12: 8-12: 200-210: 160-170: 320-340: 120-130: 5-50: 15 to 150 by mass ratio.
The invention also provides a formula of a third lithium-ion battery electrolyte containing lithium borate, which is prepared by the preparation method of the lithium-ion battery electrolyte containing lithium borate, and the lithium-ion battery electrolyte is prepared by mixing lithium hexafluorophosphate, lithium difluorooxalato borate, lithium bis (oxalato) borate, ethylene carbonate, ethyl methyl carbonate, propyl propionate, propylene carbonate, vinylene carbonate and fluoroethylene carbonate in a proportion of 130: 4-6: 6-10: 205-215: 160-170: 370-380: 80-90: 5-50: 5 to 50 by mass ratio.
Compared with the prior art, the lithium borate in the three lithium-ion battery electrolytes containing lithium borate has higher stability in a solvent, the lithium borate cannot be separated out, the turbidity phenomenon does not occur, and the quality is better.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic diagram of a first embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, the present invention provides a method for preparing a lithium ion battery electrolyte containing lithium borate, comprising the following steps:
s1, selecting a proper first solvent to carry out pretreatment on the lithium borate: heating and mixing a first solvent and lithium borate, wherein the temperature of a reaction kettle is 60-90 ℃ during mixing, the stirring time is 1-3 hours, and the first solvent can be one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, propyl propionate or dimethyl carbonate;
if ethylene carbonate is selected as a first solvent for lithium borate pretreatment, the stirring kettle needs to be kept in a heat preservation state all the time to form a mixed solution containing lithium borate;
if other substances are selected as the first solvent for lithium borate pretreatment, the mixed solution is stirred and mixed uniformly and then needs to be cooled naturally to form a mixed solution containing lithium borate;
specifically, the lithium borate in step S1 is one or two of lithium bis (oxalato) borate and lithium difluoro (oxalato) borate;
s2, preparing lithium ion battery electrolyte containing lithium borate: and (4) sequentially adding the second solvent, the mixed solution containing the lithium borate and the additive in the step S1 into the stirring kettle by calculation, mixing and stirring for 30 minutes, adding lithium hexafluorophosphate after uniformly mixing, filling and warehousing after uniformly mixing.
Specifically, the additive in step S2 is a mixture of two or more of propylene sulfate, fluoroethylene carbonate, vinylene carbonate and lithium bis-fluorosulfonylimide. The second solvent in step S2 is a mixture of three or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, dimethyl carbonate, propyl propionate, and carboxylic acid ester.
The lithium ion battery electrolyte is produced by adopting a lithium borate pretreatment method, so that the method has the advantages of not occupying the production time of mixing and stirring, greatly shortening the production process, not influencing the canning time and having high production efficiency, and the lithium borate dissolution rate and the stability in a solvent can be improved by increasing the temperature in the pretreatment, so that the excellent quality of the electrolyte is ensured.
In view of the above preparation method, this example provides the following three experimental examples.
The first experimental example:
preparing and producing 1000Kg of A-type electrolyte, adopting lithium difluoro-oxalato-borate as a lithium borate solution, adopting ethylene carbonate as a first solvent, adopting a mixture of ethylene carbonate, diethyl carbonate and propylene carbonate as a second solvent, adopting ethylene sulfate and fluoroethylene carbonate as additives, and preparing the electrolyte according to the following formula in percentage by mass:
(1) firstly, adding lithium difluoro (oxalato) borate into ethylene carbonate at the temperature of 80 +/-5 ℃, stirring and mixing uniformly to prepare a lithium difluoro (oxalato) borate mixed solution with the mass fraction of 15%, and preserving heat for later use;
(2) in the experimental example, the mass of the lithium difluoro (oxalato) borate is 10kg, the using amount m1 of a 15% lithium difluoro (oxalato) borate mixed solution is calculated, and the amount m2 of the ethylene carbonate to be supplemented is calculated;
m1＝10kg/15％＝66.67kg；
m2＝235.7kg-(m1-10kg)＝235.7kg-(66.67kg-10kg)＝179.03kg；
(3) finally, 471.4kg of diethyl carbonate, 117.9kg of propylene carbonate, m2 kg of ethylene carbonate, 15% lithium difluoroborate mixed solution containing 10kg of lithium difluoroborate, m1 kg of ethylene sulfate and 20kg of fluoroethylene carbonate are sequentially added into a reaction kettle, the materials are added and stirred for mixing, 135kg of lithium hexafluorophosphate is added at a constant speed after uniform mixing, and the mixture is filled and delivered after uniform mixing.
Because the ethylene carbonate is adopted to carry out high-temperature pretreatment on the lithium difluoro oxalate borate, the dissolving rate of the lithium difluoro oxalate borate and the stability of the lithium difluoro oxalate borate in a solvent can be improved, the lithium difluoro oxalate borate cannot be separated out, the phenomenon of turbidity does not occur, the quality is good, the excellent quality of the electrolyte is ensured, and the lithium difluoro oxalate borate high-temperature pretreatment electrolyte has the advantages of not occupying the production time of mixing and stirring, greatly shortening the production process, not influencing the canning time and having high production efficiency.
Experimental example two
Preparing and producing 1000Kg of B-type electrolyte, adopting lithium difluoro-oxalato-borate as a lithium borate solution, adopting ethylene carbonate as a first solvent, adopting ethylene carbonate, ethyl methyl carbonate, propyl propionate and propylene carbonate as a second solvent, adopting ethylene sulfate, fluoroethylene carbonate and lithium bis (fluorosulfonyl) imide as additives, and preparing the electrolyte according to the following formula in parts by mass:
(1) firstly, adding lithium difluoro (oxalato) borate into ethylene carbonate at the temperature of 80 +/-5 ℃, stirring and mixing uniformly to prepare a lithium difluoro (oxalato) borate mixed solution with the mass fraction of 15%, and preserving heat for later use;
(2) in the experimental example, the mass of the lithium difluoro (oxalato) borate is 10kg, the use amount m1 of 15% of the lithium difluoro (oxalato) borate mixed solution is calculated, and the ethylene carbonate m2 to be supplemented is calculated;
m1＝10kg/15％＝66.67kg；
m2＝206.3kg-(m1-10kg)＝206.3kg-(66.67kg-10kg)＝149.63kg；
(3) and finally, sequentially adding 165kg of ethyl methyl carbonate, m2 kg of ethylene carbonate, 330kg of propyl propionate, 123.7kg of propylene carbonate, 15% lithium difluorooxalate borate mixed solution m1 containing 10kg of lithium difluorooxalate borate, 10kg of ethylene sulfate and 15kg of fluoroethylene carbonate into the reaction kettle, stirring and mixing while adding materials, uniformly mixing, then adding 130kg of lithium hexafluorophosphate at a constant speed, stirring and mixing uniformly, and then filling and discharging.
Because the ethylene carbonate is adopted to carry out high-temperature pretreatment on the lithium difluorooxalate borate, the dissolution rate of the lithium difluorooxalate borate and the stability of the lithium difluorooxalate borate in a solvent can be improved, the lithium difluorooxalate borate cannot be separated out, the phenomenon of turbidity does not occur, the quality is good, the excellent quality of the electrolyte is ensured, and the lithium difluorooxalate borate high-temperature pretreatment device has the advantages of not occupying the production time of mixing and stirring, greatly shortening the production process, not influencing the canning time and having high production efficiency.
Experimental example III
Preparing and producing 1000Kg of C-type electrolyte, adopting lithium difluoro-oxalato-borate and lithium bis-oxalato-borate as lithium borate solutions, adopting ethylene carbonate as a first solvent, adopting ethylene carbonate, ethyl methyl carbonate, propyl propionate and propylene carbonate as a second solvent, adopting vinylene carbonate and fluoroethylene carbonate as additives, and preparing the electrolyte according to the following formula in parts by mass:
(1) firstly, adding lithium difluoro (oxalato) borate and lithium bis (oxalato) borate into ethylene carbonate at the temperature of 80 +/-5 ℃, uniformly stirring and mixing to prepare a lithium borate mixed solution containing 15% of lithium difluoro (oxalato) borate, and preserving heat for later use;
(2) in the experimental example, the mass of lithium difluoro (oxalato) borate is 5kg, the mass of lithium bis (oxalato) borate is 8kg, the using amount m1 of a lithium borate mixed solution containing 15% of lithium difluoro (oxalato) borate is calculated, and the ethylene carbonate m2 to be supplemented is calculated;
m1＝5kg/15％＝33.33kg；
m2＝209.3kg-(m1-10kg)＝209.3kg-(33.33kg-10kg)＝185.97kg；
(3) and finally, 167.4kg of ethyl methyl carbonate, m2 kg of ethylene carbonate, 376.6kg of propyl propionate, 83.7kg of propylene carbonate, a lithium borate mixed solution m1 containing 5kg of lithium difluorooxalate borate and 8kg of lithium bis-oxalate borate, 10kg of vinylene carbonate and 10kg of fluoroethylene carbonate are sequentially added into a reaction kettle, the materials are added and stirred while being mixed, 130kg of lithium hexafluorophosphate is added at a constant speed after uniform mixing, and the materials are filled and delivered after uniform mixing.
Because the ethylene carbonate is adopted to carry out high-temperature pretreatment on the lithium difluoro oxalate borate and the lithium bis-oxalate borate, the dissolving rate and the stability in a solvent of the lithium difluoro oxalate borate and the lithium bis-oxalate borate can be improved, the lithium difluoro oxalate borate and the lithium bis-oxalate borate do not have a turbid phenomenon, the quality is good, the excellent quality of the electrolyte is ensured, and the method has the advantages of not occupying the production time of mixing and stirring, greatly shortening the production process, not influencing the canning time and having high production efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of lithium borate-containing lithium ion battery electrolyte is characterized by comprising the following steps:
s1, selecting a proper first solvent to carry out pretreatment on the lithium borate: heating and mixing a first solvent and lithium borate, wherein the temperature of a reaction kettle is 60-90 ℃ during mixing, the stirring time is 1-3 hours, and the first solvent is one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, propyl propionate or dimethyl carbonate;
if ethylene carbonate is selected as a first solvent for lithium borate pretreatment, the stirring kettle needs to be kept in a heat preservation state all the time to form a mixed solution containing lithium borate;
if other substances are selected as the first solvent for lithium borate pretreatment, the mixed solution is stirred and mixed uniformly and then needs to be cooled naturally to form a mixed solution containing lithium borate;
s2, preparing lithium ion battery electrolyte containing lithium borate: and (4) sequentially adding the second solvent, the mixed solution containing the lithium borate and the additive in the step S1 into the stirring kettle by calculation, mixing and stirring for 30 minutes, adding lithium hexafluorophosphate after uniformly mixing, filling and warehousing after uniformly mixing.
2. The method according to claim 1, wherein the lithium borate in step S1 is one or a mixture of two of lithium bis (oxalato) borate and lithium difluoro (oxalato) borate.
3. The method of claim 1, wherein the additive in step S2 is a mixture of two or more of propylene sulfate, fluoroethylene carbonate, vinylene carbonate and lithium bis-fluorosulfonylimide.
4. The method of claim 1, wherein the second solvent in step S2 is a mixture of three or more selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, propyl propionate, dimethyl carbonate, and carboxylic acid ester.
5. The method according to any one of claims 1 to 4, wherein the first solvent in step S1 is ethylene carbonate.
6. The method of claim 5, wherein the second solvent in step S2 is a mixture of ethylene carbonate, diethyl carbonate and propylene carbonate.
7. The method of claim 5, wherein the second solvent in step S2 is selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, propyl propionate, and propylene carbonate.
8. A formulation of a lithium-ion battery electrolyte containing lithium borate, characterized in that it is prepared by the method of any one of claims 1 to 7 for the preparation of a lithium-ion battery electrolyte containing lithium borate, from lithium hexafluorophosphate, lithium difluorooxalato borate, ethylene carbonate, diethyl carbonate, propylene carbonate, ethylene sulfate and fluoroethylene carbonate in a ratio of 135: 8-12: 230-240: 465-475: 115-125: 5-50: 10 to 100 by mass ratio.
9. A formulation of a lithium-ion battery electrolyte containing lithium borate, characterized in that it is prepared by the method of any one of claims 1 to 7 for the preparation of a lithium-ion battery electrolyte containing lithium borate, which is prepared from lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide, ethylene carbonate, ethyl methyl carbonate, propyl propionate, propylene carbonate, ethylene sulfate and fluoroethylene carbonate in a ratio of 130: 8-12: 8-12: 200-210: 160-170: 320-340: 120-130: 5-50: 15 to 150 by mass ratio.
10. A formulation of a lithium-ion battery electrolyte containing lithium borate, characterized in that it is prepared by the method of any one of claims 1 to 7 for the preparation of a lithium-ion battery electrolyte containing lithium borate, which is prepared from lithium hexafluorophosphate, lithium difluorooxalato borate, lithium bis-oxalato borate, ethylene carbonate, ethyl methyl carbonate, propyl propionate, propylene carbonate, vinylene carbonate and fluoroethylene carbonate in a ratio of 130: 4-6: 6-10: 205-215: 160-170: 370-380: 80-90: 5-50: 5 to 50 by mass ratio.
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